Method for preparing nitronitrites and dinitroparaffins from alpha-olefins



United States Patent 3,192,248 METHOD FOR PREPARING NITRONITRITES ANDDINITROPARAFFINS FROM ALPHA-OLEFINS Giovanni A. Bonetti, Wilmington,DeL, Chester 13. de

Savigny, Rancho Cordova, Calif., and Conrad Michalski, Media, andRudolph Rosenthal, Broomall, Pa., assignors to The Atlantic RefiningCompany, Philadelphia, Pa., a corporation of Pennsylvania No Drawing.Filed Feb. 26, 1964, Ser. No. 347,398 17 Claims. (Cl. 260-467) Thisapplication is a continuation-in-part of our co pending application,Serial No. 224,731, filed September 19, 1962, entitledNitrogen-Containing Derivatives of Alpha-Olefins, now abandoned.

This invention relates to a method for preparing nitronitrites anddinitroparatfins from alpha-olefins and, more particularly, it relatesto a method for preparing ni ronitrites having the formula R-CH-CHrNOaand dinitroparaflins having the formula wherein R is a normal alkylradical containing from 1 to 22 carbon atoms.

Considerable progress has been made in the synthesis, separation, andrecovery of nitrogen-containing aliphatic compounds. However, work inthis area has been concerned primarily with the production ofmono-nitroparaffins by the vapor phase reactions of various alkanes withnitrating agents, including I-INO NO, N0 and N 0 Additional work hasbeen carried out on the nitration of olefins utilizing N 0 either in theabsence of a solvent or in the presence of ester or ether solventsdescribed as the complexing type. In carrying out these reactions,relatively low temperatures have been employed, i.e., from about 25 C.to 30 C. in the liquid phase. It has been found under these conditionsthat comparatively large quantities of by-products are formed with theresult that the maximum yields of the desired nitronitrites anddinitroparafiins are limited to 75 to 85 percent. Moreover, theby-products which are formed frequently interfere with the subsequentconversion of the nitronitrites and dinitroparaflins into the desirednitrogen containing products such as the nitroalcohols and nitroolefins.

The present invention is directed to a method for the preparation ofnitrogen-containing compounds from alphaolefins, which compounds may beutilized in the synthesis of other desirable nitrogen contaningcompounds; e.g., nitroalcohols and nitroolefins, wherein the alkyl groupof the compound is straight chain. In particular, the invention isdirected to the preparation of mixtures of nitronitrites anddinitroparafiins, in substantially quantitative yields.

It is, therefore, an object of this invention to provide a process forthe nitration of normal alpha-olefins.

It is a further object of this invention to provide a process for thenitration of normal alpha-olefins with an equilibrium mixture of N0 andN 0 to produce a mixture of nitronitrites and dinitroparaflins insubstantially quantitative yields.

Other objects of this invention will'be apparent from the descriptionand claims that follow.

As used in this specification and appended claims, the

3,192,248 Patented June 29, 1965 term nitronitrites means compoundshaving the formula wherein R is a normal alkyl radical containing from 1to 22 carbon atoms; the term nitroalcohols means compounds having theformula wherein R is a normal alkyl radical containing from 1 to 22carbon atoms; and the term nitroolefins means compounds having theformula RCH=CHNO wherein R is a normal alkyl radical containing from 1to 22 carbon atoms.

In accordance with this invention a normal alpha-olefin (a mono-olefinwith a terminal double bond) containing from 3 to 24 carbon atoms, or amixture of these, is dissolved in a parafiinic hydrocarbon solvent andthereafter contacted with an equilibrium mixture of N0 and N 0,. Theparafiinic hydrocarbon solvent ranges from 20 volume percent to 99volume percent of the solution; preferably, however, from 50 volumepercent to volume percent of the solution. The equilibrium mixture of N0and N 0 may be contacted with the alphaolefin in the solvent either in abatch reaction or a continuous reaction.

In the batch-type reaction the normal alpha-olefin dissolved in thesolvent is placed in a reaction vessel and the gaseous equilibriummixture of N0 and N 0 is bubbled into the solution with sufiicientagitation to provide thorough contacting. Upon completion of thereaction the solvent and any excess nitrating agent may be removed fromthe products by distillation or the excess nitrating agent is strippedfrom the product-solvent mixture with nitrogen, helium or similar inertgas which will not react either with the products or with the N0 and N0,. The latter procedure is employed when. it is desired to retain thenitronitrite-dinitroparafiin product in the solvent as a solution forsubsequent processing.

In the continuous reaction system the alpha-olefin dissolved in theparaffinic solvent is introduced into the top of a packed column ortower along with the equilibrium mixture of N0 and N 0 The gas andliquid are allowed to come in contact while passing downwardly over thepacking in the column and the products dissolved in the solvent areremoved from the bottom of the column. If desired, the solvent and anyexcess nitrating agent may be removed by distillation or the efiiuentfrom the reactor column may be passed into a stripping column where theexcess N0 and N 0 are stripped from the solution with nitrogen orsimilar inert gas as has been described leaving the products insolution.

The amount of equilibrium mixture of N0 and N 0 may vary Within widelimits. It has been found that satisfactory results are obtained whenthe amount of equilibrium mixture used ranges between about 0.5 mole permole of normal alpha-olefin and 2.4 moles per mole of normalalpha-olefin. Although amounts less than one mole of equilibrium mixtureper mole or normal alphaolefin will result in unreacted olefin in theproduct, the

reaction is substantially quantitative with respect to the olefinconverted and thus less than the mole-per-mole ratio of equilibriummixture to normal alpha-olefin may be used without producing undesiredby-products. Moreover, amounts in excess of 2.4 moles of mixture permole of normal alpha-olefin may be used, however, no noticeableimprovements are apparent.

The nitration reaction occurs with extreme rapidity and therefore thetime of contact between the olefin and nitrating agent may be veryshort, i.e., 0.1 second. Since the reaction is exothermic, however, itis preferable in order to control the reaction temperature, to employtimes of from 15 to 60 seconds in a continuous column reaction systemand generally from about 3 minutes to 10 minutes for the time ofaddition of the nitrating agent to the olefin in a batch reactionsystem. Thus the contact time may be in the range of from 0.1 second to10 minutes.

It is advantageous that the reaction temperature be at least 50 C. inorder to preclude the production of nitronitrates, ketones, aldehydesand mononitroparafiins, since such products interfere with subsequentseparation steps. The temperature may range up to about 150 C. Thepreferred temperature range is from 50 C. to 90 C.

The parafiinic hydrocarbon solvent may be a normal, cyclic or branchedhydrocarbon having from 6 to 24 carbon atoms in the molecule, preferablyfrom 6 to 15 carbon atoms, or mixtures of such hydrocarbons. Examples ofsuch hydrocarbons which may be used as solvents are nhexane,cyclohexane, methylcyclohexane, n-heptane, noctane iso-octane, n-nonane,n-decane, undecanes, dodecanes, tridecanes, tetradecanes, pentadecanes,hexadecanes and similar paraflinic hydrocarbons.

When the nitration is carried out in accordance with this methodutilizing the described parafiinic hydrocarbon solvent there is produceda mixture of nitronitrites and dinitroparafiins in about a 1:1 weightratio. It has also been found that these compounds are essentially theonly compounds produced and therefore the reaction is substantiallyquantitative based on the alpha-olefin charge. The nitronitrites anddinitroparaffins, although they may be recovered by distilling off thesolvent and any nitrating agent remaining in the solvent productreaction mixture, are preferably retained in the parafiinic hydrocarbonsolvent as a solution since they are conveniently handled in this formfor the subsequent hydrolysis steps leading to their conversion to othernitrogen derivatives to be described. The N and N 0 mixture which isstripped from the solution may be recovered and reused.

The nitronitrites and dinitroparafiins have utility as intermediates inthe production of other nitrogen containing compounds, thus, the mixtureof nitronitrites and dinitroparaffins may be hydrolyzed at a temperatureranging between ambient temperatures and 100 C. for a period of timeranging between 1 minute and 2 hours in the presence of an aliphaticalcohol containing from 1 to 6 carbon atoms or a mixture of such analcohol with water or with water alone. The quantity of alcohol,alcohol-water or water required to hydrolyze this mixture ranges from aminimum of 1 mole per mole of the nitronitrite up to 20 moles or more ofthe hydrolyzing agent. There is produced in this hydrolysis reaction amixture of nitroalcohols and dinitroparafi'ins in about a 1:1 weightratio, i.e., only the nitronitrites are hydrolyzed.

The mixture of nitroalcohols and dinitroparafins from the hydrolysisstep may be separated by any conventional method such as by silica gelchromatography. For example, upon passage of a solution of thenitroalcohols and dinitroparafiins contained in 2,2,4-trimethylpentane(isooctane) through a column of silica gel which previously has beenwetted with 2,2,4-trimethylpentane, the nitroalcohols anddinitroparafiins are adsorbed on the silica gel. The dinitroparafiinsare removed first from the silica gel by elutriation with benzene. Thenitroalcohols are subsequently removed from the silica gel byelutriation with diethyl ether. The dinitroparaflins are recovered byevapo- 4 rating the benzene, and the nitroalcohols are recovered byevaporating the diethyl ether.

It has been found that the dinitroparaffins may be converted to thecorresponding nitroolefins by hydrolyzing with an aqueous slurry of aGroup II oxide, such as calcium oxide or magnesium oxide. The time oftreatment ranges from about 10 minutes to about 1 hour, preferably fromabout 10 minutes to about 30 minutes. The reaction may be carried out atambient or somewhat higher temperatures.

The nitroalcohols may be dehydrated to the corresponding nitroolefins bycontacting them with an alcoholic alkali metal hydroxide solution. Thetotal amount of alcoholic alkali metal hydroxide solution used mustcontain at least a stoichiometric amount of alkali metal hydroxide basedon the amount of nitroalcohol to be converted and may contain up toabout three times the stoichiometric amount or more, although noadvantages are apparent for such higher amounts. The alcohol used inpreparing the alcoholic alkali metal hydroxide solution may contain from1 to 3 carbon atoms, preferably methyl or ethyl alcohol. Preferredalkali metal hydroxides are sodium hydroxide, and potassium hydroxide,with sodium hydroxide being the most preferred.

The following examples are provided to further illustrate the invention.In Examples I to VII, inclusive, a continuous reactor system wasemployed wherein the alpha-olefin solution in a parafiinic hydrocarbonsolvent was passed downwardliy over glass bead packing in the column andtherein contacted with an equilibrium mixture of N0 and N 0 The contacttimes were in the range of from about 15 seconds to about 1 minute.Examples VIII and IX were batch reactions.

Example 1 Into ml. of 2,2,4-trimethylpentane there was passed 1.76 molesof propylene and 0.92 mole of equilibrium mixture of N0 and N 0 at atemperature of 52 C. Upon evaporation of the 2,2,4-trimethylpentane andexcess nitrating agent, infrared analysis of the reaction product showedthat there was produced l-nitro-2-propanolnitrite and 1,2-dinitropropanein about a 1:1 weight ratio. The product mixture was stirred with 200ml. of methanol at ambient temperature for 25 minutes. There wasrecovered 16.5 grams of product which upon infrared analysis wasidentified as 1-nitro-2-propanol and 1,2-dinitropropane.

Example II In 200 ml. of 2,2,4-trimethylpentane there was dissolved 0.25mole of hexene-l. The solution was contacted with 0.58 mole ofequilibrium mixture of N0 and N 0 at a temperature of 55 C. Uponevaporation of the 2,2,4-trimethylpentane and excess nitrating agent,infrared analysis of the product (41.7 grams) showed that there wasproduced only l-nitro-2-hexanolnitrite and 1,2- dinitrohexane in about a1:1 weight ratio. The total product mixture was hydrolyzed overnightwith 200 ml. of methanol at ambient temperature. Ten grams of thehydrolyzed product after removal of solvent and hydrolyzing agent wasseparated and there was recovered 4.4 grams of 1,2-dinitrohexane and5.14 grams of 1- nitro- 2-hexanol.

Example III In 360 ml. of 2,2,4-trimetl1ylpentane there was dissolved0.9 moles of octene-l. The solution was contacted with 1.92 moles ofequilibrium mixture of N0 and N 0 at a temperature of 52 C. Uponevaporation of the 2,2,4- trimethylpentane and excess nitrating agent,infrared analysis of the product (183.6 grams) showed that there wasproduced only 1-nitro-2-octanol nitrite and 1,2-dinitrooctane in about a1:1 weight ratio. To 29.7 grams of this product mixture there was added20 ml. of 2,2,4- trimethylpentane. The mixture was heated to 70 C. Water(50 ml.) was added and the mixture was heated to 83 C. over a ten-minuteperiod. Infrared'analysis showed that 48.8 weight. percentl-nitro-Z-octanol and 50.5 weight percent 1,2-dinitrooctane wereproduced.

Example IV maintained at 70 C. to 75 C. The excess nitrating agent wasremoved from the reactor effluent by means of a stream of nitrogen gas.The stripped eflluent was then hydrolyzed with water at a temperature ofabout 80 C. for approximately 30 minutes. The aqueous layer wasseparated and the organic layer was stripped free of solvent undervacuum. The product obtained from the hydrolysis reaction analyzed: 52.1weight percent of 1-nitrohexadecanol-2; 46.5 weight percent of 1,2-dinitrohexadecane; 0.2 weight percent of l-nitrohexadecyl nitrate-2 andapproximately 0.2 weight percent unidentified carbonyl compounds. Nohexadecene-l, nitroolefin or nitronitrite was found in the product.These results show that the nitration step produced substantiallyquantitative yields of 1-nitro-2-hexadecanol nitrite and 1,2-dinitrohexadecane.

Example V Pure hexadecene-l in the absence of a solvent was passed intothe same column described in Example IV, along with the same amount ofnitrating agent and at the same rate as described in Example IV. Thereaction temperature was also maintained at 75 C. and excess nitratingagent was stripped from the product with nitrogen. The stripped productwas hydrolyzed with water in a manner similar to that described inExample IV. The product obtained following the hydrolysis analyzed 41.6weight percent of l-nitrohexadecanol-Z; 45.3 Weight percent of1,2-dinitrohexadecane; 1.4 weight percent of 1-nitrohexadecylnitrate-2;3.1 weight percent l-nitrohexadecene-l and approximately 3.5 weightpercent unidentified carbonyl compounds. The comparison of the resultsfrom this example with Example 1V clearly demonstrates that the use of aparaflinic hydrocarbon solvent provides the means of obtainingquantitative yields of the desired nitronitrites and dinitroparafiins.

Example VI In 100 ml. of 2,2,4-trimethylpentane there was dissolved0.114 mole of docosene-l. The solution was contacted with 0.26 mole ofequilibrium mixture of N0 and N 0 at a temperature of 54 C. Uponevaporation of the 2,2,4-trimethylpentane and excess nitrating agent,infrared analysis showed that there was produced only 1-nitro-2-docosanol nitrite and 1,2-dinitrodocosane in about a 1:1 weight ratio.

Example VII In 100 ml. of cyclohexane there was dissolved grams ofoctene-l. This solution was passed with an equilibrium mixture of N0 andN 0 (0.2 mole) at a rate of 3.2 ml. per minute through a columnmaintained at 50 C. to 55 C. The product, 16.55 grams, was shown to beidentical with that obtained in Example III.

Example VIII Into a 500 ml. three-nicked flask were introduced 23.7grams of decene-l and 200 ml. of n-decane. The solution was heated to140 C. and an equilibrium mixture of N0 and N 0 was passed intothesolution in an amount sufiicient to nitrate all of the decene-l whilethe solution was stirred and over a period of about 10 minutes. Afterhydrolysis of the product with water, the

infrared analysis showed that it contained 1-nitrodecanol-Z and1,2-dinitrodecane in about a 1:1 weight ratio.

Example IX Into a 500 ml. three-necked flask were introduced 28 grams(0.25 mole) octene-l and 300 ml. n-heptane. While the solution wasstirred and maintained at a temperature of 70 C. to C., 19 grams (0.205mole) of an equilibrium mixture of N0 and N 0 were passed in over aperiod of about 10 minutes. After removing the solvent and excess olefinby vacuum distillation, infrared analysis of the product showed itcontained l-nitro- Z-octanolnitrite and 1,2-dinitrooctane in about a 1:1weight ratio.

Example X A column of silica gel 3 feet high and 1 inch in diameter waswetted with 250 ml. of 2,2,4-trimethylpentane. All 11.4 gram mixture of1-nitro-2-octanol and 1,2-dinitrooctane as prepared in accordance withExample 111 was dissolved in 50 ml. of 2,2,4-trimethylpentane andabsorbed. onto the silica gel column. Upon passage of 750 ml. of benzenethrough the column and evaporation of the benzene there was recovered4.9 grams of 1,2-dinitrooctane which was identified by infraredanalysis. Upon subsequent passage of 500 ml. of diethyl ether throughthe column and evaporation of the ether, there was recovered 5.2 gramsof l-nitro-Z-octanol which was identified by infrared analysis. Thisexperiment demonstrates that the mixture produced in accordance withthis invention may be separated by conventional methods.

From the foregoing examples, it has been demonstrated that normalalpha-olefins including those which are normally gaseous, liquid andsolid, may be nitrated substantially quantitatively to a mixture of thecorresponding nitronitrites and dinitroparafiins by the use of aparafiinic hydrocarbon solvent and elevated temperatures in accordancewith this invention.

The nitrogen-containing derivatives of alpha-olefins prepared inaccordance with this invention are useful as chemical intermediates ashas been described, and in the production of other useful products bymethods Wellknown to the art. The dinitroparaffins are useful assolvents and plasticizers, particularly for nitro-cellulose, and as hasbeen described, the dinitroparafiins may be hydrolyzed to producenitroolefins, which, in turn, are useful in the preparation of polymericmaterials. The dinitroparaflins may be reduced by known methods to thecorresponding diaminoparaffins and the diaminoparafiins, in turn, areuseful in the preparation of polyamide resins, as crosslinking agentsfor epoxy resins and as solvents. The nitronitrites, because of theirinstability, are preferably hydrolyzed to the corresponding nitroalcohols. The nitroalcohols, in turn, are exceedingly useful since theymay be converted to anionic detergents by sulfation or non-anionicdetergents by condensation with an alkylene Oxide such as ethyleneoxide. The nitroalcohols also are useful as solvents and plasticizers,particularly for nitrocellulose.

We claim:

1. A method for preparing nitronitrites having the formula anddinitroparalnns having the formula wherein R is a normal alkyl radicalcontaining from -1 to 22 carbon atoms which comprises contacting anormal alpha-olefin having from 3 to 24 carbon atoms in the molecule anddissolved in a parafiinic hydrocarbon solvent having from 6 to 24 carbonatoms in the molecule with a nitrating agent consisting of anequilibrium mixture of N and N 0 at a temperature in the range from 50C. to 150 C. and thereafter recovering the nitronitrite anddinitroparafiin product.

2. The method according to claim 1 wherein the temperature is in therange from 50 C. to 90 C.

3. The method according to claim 1 wherein the parafiinic hydrocarbonsolvent has from 6 to 15 carbon atoms in the molecule.

4. A method for preparing nitronitrites having the formula anddinitroparaflins having the formula R-CH-CHTNO;

wherein R is a normal alkyl radical containing from 1 to 22 carbon atomswhich comprises contacting a normal alpha-olefin having from 3 to 24carbon atoms in the molecule and dissolved in a parafiinic hydrocarbonsolvent having from 6 to 24 carbon atoms in the molecule with anitrating agent consisting of an equilibrium mixture of N0 and N 0 at atemperature in the range from 50 C. to 150 C. and thereafter recoveringthe nitronitrite and dinitroparaffin product by distilling said solventand remaining nitrating agent therefrom.

5. The method according to claim 4 wherein the temperature is in therange from 50 C. to 90 C. and the paraffinic hydrocarbon solvent hasfrom 6 to 15 carbon atoms in the molecule.

6. A method for preparing nitronitrites having the formula anddinitroparafiins having the formula werein R is a normal alkyl radicalcontaining from 1 to 22 carbon atoms which comprises contacting a normala1pha-olefin having from 3 to 24 carbon atoms in the molecule anddissolved in a paratfinic hydrocarbon solvent having from 6 to 24 carbonatoms in the molecule with a nitrating agent consisting of anequilibrium mixture of N0 and N 0 at a temperature in the range from 50C. to 150 C., stripping the remaining nitrating agent from the solutionof the reaction products with an inert gas and recovering the solutionof nitronitrite and dinitroparafiin product in said paraflinichydrocarbon solvent.

7. The method according to claim 6 wherein the temperature is in therange from 50 C. to 90 C. and the paraifinic hydrocarbon solvent hasfrom 6 to 15 carbon atoms in the molecule.

8. A method for preparing 1-nitro-2-propano1 nitrite and1,2-dinitropropane which comprises contacting propylene dissolved in aparafiinic hydrocarbon solvent having from 6 to 15 carbon atoms in themolecule with a nitrating agent consisting of an equilibrium mixture ofN0 and N 0 at a temperature in the range of from 50 C. to 90 C. andthereafter recovering the 1-nitro-2- propanolnitrite and1,2-dinitropropane by distilling the solvent and remaining nitratingagent therefrom.

9. A method for preparing 1-nitr0-2-propanol nitrite and1,2-dinitropropane which comprises contacting propylene dissolved in aparaffinic hydrocarbon solvent having from 6 to 15 carbon atoms in themolecule with a nitrating agent consisting of an equilibrium mixture ofN0 and N 0 at a temperature in the range of from 50 C. to C., strippingthe remaining nitrating agent from the solution of the reaction productswith an inert gas and recovering the solution of1-nitro-2-propanolnitrite and 1,2-dinitropropane in said parafiinichydrocarbon solvent.

10. A method for preparing 1-nitro-2-hexanol-nitrite and1,2-dinitrohexane which comprises cont-acting hexene-l dissolved in aparaffinic hydrocarbon solvent having from 6 to 15 carbon atoms in themolecule with a nitrating agent consisting of an equilibrium mixture ofN0 and N 0 at a temperature in the range of from 50 C. to 90 C. andthereafter recovering the l-nitro- 2-hexanolnitrite and1,2-dinitrohexane by distilling the solvent and remaining nitratingagent therefrom.

11. A method for preparing 1-nitro-2-hexanolnitrite and1,2-dinitrohexane which comprises contacting hexene-l dissolved in aparafrinic hydrocarbon solvent having from 6 to 15 carbon atoms in themolecule with a nitrating agent consisting of an equilibrium mixture ofN0 and N 0 at a temperature in the range of from 50 C. to 90 C.,stripping the remaining nitrating agent from the solution of thereaction products with an inert gas and recovering the solution ofl-nitro-Z-hexanolnitrite and 1,2-dinitrohexane in said paraffinichydrocarbon solvent.

12. A method for preparing 1-nitro-2-octanolnitrite and1,2-dinitrooctane which comprises contacting octene-l dissolved in aparafinic hydrocarbon solvent having from 6 to 15 carbon toms in themolecule with a nitrating agent consisting of an equilibrium mixture ofN0 and N 0 at a temperature in the range of from 50 C., to 90 C. andthereafter recovering the 1-nitro-2-octanolnitrite and 1,2-dinitrooctane by distilling the solvent and remaining nitrating agenttherefrom.

13. A method for preparing 1-nitro-2-octanolnitrite and1,2-dinitrooctane which comprises contacting octene-l dissolved in aparafiinic hydrocarbon solvent having from 6 to 15 carbon atoms in themolecule with a nitrating agent consisting of an equilibrium. mixture ofN0 and N 0 at a temperature in the range of from 50 C. to 90 C.,stripping the remaining nitrating agent from the solution of thereaction products with an inert gas and recovering the solution of1-nitro-2-octanolnitrite and 1,2- dinitrooctane in said paraflinichydrocarbon solvent.

14. A method for preparing 1-nitro-2-hexadecanolnitrite and1,2-dinitrohexadecane which comprises contacting hexadecene-l dissolvedin a paraflinic hydrocarbon solvent having from 6 to 15 carbon atoms inthe molecule with a nitrating agent consisting of an equilibrium mixtureof N0 and N 0 at a temperature in the range of from 50 C. to 90 C. andthereafter recovering the 1- nitro-2-hexadecanolnitrite and1,2-dinitrohexadecane by idistilling the solvent and remaining nitratingagent there- 15. A method for preparing l-nitro-2-hexadecanolnitrite and1,2-dinitrohexadecane which comprises contacting hexadecene-l dissolvedin a paraffinic hydrocarbon solvent having from 6 to 15 carbon atoms inthe molecule with a nitrating agent consisting of an equilibrium mixtureof N0 and N 0 at a temperature in the range of from 50 C. to 90 C.,stripping the remaining nitrating agent from the solution of thereaction products with an inert gas and recovering the solution ofl-nitro-Z-hexadecanolnitrite and 1,2-dinitrohexadecane in saidparafiinic hydrocarbon solvent.

16. A method for preparing 1-nitro-2-docosanolnitrite and1,2-dinitrodocosane which comprises contacting docosene-l dissolved in aparaffinic hydrocarbon solvent having from 6 to 15 carbon atoms in themolecule with a nitrating agent consisting of an equilibrium mixture ofN0 and N 0 at a temperature. in the range of from 50 C. to 90 C. andthereafter recovering the 1-nitro-2- docosanolnitrite and1,2-dinitrodocosane by distilling the the solvent and remainingnitrating agent therefrom.

17. A method for preparing 1-nitro-2-docosanoln1'trite and1,2-dinitrodocosane which comprises contacting docosene-l dissolved in aparafiinic hydrocarbon solvent having from 6 to 15 carbon atoms in themolecule with a nitrating agent consisting of an equilibrium mixture ofN0 and N 0 at a temperature in the range of from 50 C. to 90 C.,stripping the remaining nitrating agent from the solution of thereaction products with an inert gas and recovering the solution of1-nitro-2-d0cosano1- nitrite and 1,2-dinitrodocosane in said parafiinichydrocarbon solvent.

No references cited.

10 REUBEN EPSTEIN, Acting Primary Examiner.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent Nos 3 l92248 June 29, 1965 Giovanni A; Bonetti et ale Column 2, line 71, for "or"read of column 5, line 6, for "2,2,4-trimethylpentene" read2,2,4-trimethylpentane line 69, for "three-nicked" read three-neckedcolumn 6, lines 21 and 22, for "absorbed" read adsorbed Signed andsealed this 21st day of December 1965.,

(SEAL) Attest:

ERNEST W. SWIDER EDWARD J. BRENNER Attesting Officer Commissioner ofPatents

1. A METHOD FOR PREPARING NITRONITRITES HAVING THE FORMULA